Allyl bromide → HCID 67929865, compound

HRID 2248196Notes

Reaction equation

HRID 2248196 reaction equation
[O:1]([CH2:8][C:9]([NH:11][CH:12]1[C:23](=[O:24])[N:14]2[C:15]([C:20]([O-:22])=[O:21])=[C:16]([CH3:19])[CH2:17][S:18][C@H:13]12)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na+].S([O-])([O-])(=O)=O.[OH-].[CH2:32]([N+](CCCC)(CCCC)CCCC)[CH2:33][CH2:34]C.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.[OH-].[Na+].C(Br)C=C>C(Cl)Cl.O>[O:1]([CH2:8][C:9]([NH:11][CH:12]1[C:23](=[O:24])[N:14]2[C:15]([C:20]([O:22][CH2:34][CH:33]=[CH2:32])=[O:21])=[C:16]([CH3:19])[CH2:17][S:18][C@H:13]12)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 7841Allyl bromide2×HCID 14798Sodium HydroxideHCID 67929911HCID 67929911, compoundHCID 131716462HCID 131716462, compound

Product 1

HCID 67929865HCID 67929865, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
50 °C

Procedure

The solution of sodium 7-phenoxyacetylamino-3-methyl-3-cephem-4-carboxylate was added to a solution of 71.3 g (210 mmole) of tetra-n-butylammonium hydroxide sulfate in 700 ml of methylene chloride and 700 ml of water which had been readjusted to pH 7.5 with 2N sodium hydroxide. The mixture was stirred for about 5 minutes and the methylene chloride layer was separated. The aqueous phase was extracted twice with methylene chloride and the extracts were combined with the organic layer. The organic layer was dried over magnesium sulfate and evaporated to a brown oil. The oil was dissolved in 250 ml of chloroform and 34.6 ml (400 mmole) of allyl bromide (previously filtered through activated alumina) were added with stirring. The mixture was stirred for about 19 hours at room temperature and when thin layer chromatography indicated some remaining starting material, 17 ml of allyl bromide were added and the mixture was heated to 50° C. with stirring for about 2 hours. The reaction mixture was evaporated on a rotary evaporator to remove chloroform and the concentrate was dissolved in 3:1, v:v of diethyl ether:methylene chloride and the solution extracted twice with pH 7 buffer, once with brine and was dried over magnesium sulfate. The solution was evaporated under vacuum to provide allyl 7-phenoxyacetylamino-3-methyl-3-cephem-4-carboxylate as a crude yellow solid.

Workup

  1. customthe methylene chloride layer was separated
  2. extractionThe aqueous phase was extracted twice with methylene chloride
  3. dry with materialThe organic layer was dried over magnesium sulfate
  4. customevaporated to a brown oil
  5. dissolutionThe oil was dissolved in 250 ml of chloroform
  6. additionwere added
  7. stirringwith stirring
  8. stirringThe mixture was stirred for about 19 hours at room temperature
  9. additionwere added
  10. stirringwith stirring for about 2 hours
  11. customThe reaction mixture was evaporated on a rotary evaporator
  12. customto remove chloroform
  13. dissolutionthe concentrate was dissolved in 3:1, v
  14. extractionv of diethyl ether:methylene chloride and the solution extracted twice with pH 7 buffer
  15. dry with materialonce with brine and was dried over magnesium sulfate
  16. customThe solution was evaporated under vacuum

Sources & evidence

ORD record
ord-752423339d4a40da8e0f834322f83b29
Source dataset
uspto-grants-1991_08
Patent number
US05037975

Reaction notes

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